Composite of metal and resin and method for manufacturing same

ABSTRACT

A composite of a metal part and a resin composition part that is improved so that the metal and resin are integrally joined to have strong bonding properties, and a method for manufacturing the composite. A magnesium alloy part is inserted into a mold, a resin composition is injected and joined to the part, and a composite is obtained. A part having, formed thereon, a surface layer of a metal oxide, a metal carbonate, or a metal phosphate in use of a usual conversion treatment or a modification method thereof can be used for the magnesium alloy plate  1 . The surface that has a larger amount of crystal-like objects of a nanolevel on the surface layer composed of the metal oxide, metal carbonate, or metal phosphate has a higher level of hardness, microscopic roughness, and good injection joining force, and these parameters can be controlled by a conversion treatment method. A resin composition  4 , containing PBT or PPS as the main component, is used as the resin composition part.

TECHNICAL FIELD

The present invention relates to a composite of a metal and a resin thatis composed of a metal and a resin composition suitable for casings ofelectronic devices, housings of home electric appliances, structuralcomponents, machinery parts, and the like, and also to a method formanufacturing the composite. More specifically, the present inventionrelates to a composite in which a base material made from a magnesiumalloy that has been produced by various types of mechanical processingand a thermoplastic resin composition are integrated to be laminated,and also to a method for manufacturing the composite. Thus, the presentinvention relates to a composite of a metal and a resin that is suitablefor various electronic devices, electric apparatuses, medical devices,automobiles, railroad trains, aircrafts, vehicle-mounted parts,structural components such as building materials and external trimparts.

BACKGROUND ART

A technology for integrating metals and synthetic resins is needed in awide range of industrial fields including the production of parts forautomobiles, domestic electric appliances, industrial machinery, and thelike, and a large number of adhesives have been developed therefor.Among them, excellent adhesives have been developed. For example,adhesives demonstrating adhesive functions at normal temperature orunder heating are used for integrally joining metals and syntheticresins, and such a method is presently a generally employed joiningtechnology.

However, more rational joining methods that use no adhesives have alsobeen studied. An example of such methods is a method for integratinghigh-strength engineering plastics, without using an adhesive, withlight metals such as magnetism, aluminum, and alloys thereof or ironalloys such as stainless steel. For example, the inventors havesuggested a method for injecting a molten resin onto a metal part thathas been inserted in advance into an injection molding mold, molding theresin part and simultaneously fixing (joining) the molded part and themetal part (this method will be referred to hereinbelow as “injectionjoining”).

This invention suggests a manufacturing technology by which apolybutylene terephthalate resin (referred to hereinbelow as “PBT”) or apolyphenylenes sulfide resin (referred to hereinbelow as “PPS”) isinjection joined to an aluminum alloy (for example, see Patent Document1). A joining technology has also been suggested by which a large holeis provided in an anodization film on an aluminum material and bondingis performed by filling the hole with a synthetic resin body (forexample, see Patent Document 2).

The principle of the injection joining suggested in the Patent Document1 will be explained below. An aluminum alloy is immersed into a diluteaqueous solution of a water-soluble amine compound, and the aluminumalloy is finely etched by a weak basicity of the aqueous solution.Further, it has been found that the adsorption of the amine compoundmolecules on the aluminum alloy surface simultaneously occurs during theimmersion. The aluminum alloy subjected to such treatment is placed asan insert into an injection molding mold and a molten thermoplasticresin is injected under a high pressure.

In this case, heat is generated by the interaction of the thermoplasticresin and amine compound molecules adsorbed on the aluminum alloysurface. Almost simultaneously with this heat generation, thethermoplastic resin comes into contact with the aluminum alloy that hasbeen held at a low temperature of the mold and is rapidly cooled. As aresult, solidification of the resin that has to crystallize and solidifyis delayed and it penetrates into ultrafine concavities present on thealuminum alloy surface. As a consequence, the aluminum alloy andthermoplastic resin are strongly joined (fixed), so that the resin doesnot peel from the aluminum alloy surface. Thus, where the exothermalreaction occurs, strong injection joining becomes possible. It hasactually been confirmed that PBT or PPS that can participate inexothermal reactions with amine compounds can be injection joined toaluminum alloys.

Patent Document 1: Japanese Patent Application laid open No. 2004-216425

Patent Document 2: International Patent Application WO2004/055248 A1

DISCLOSURE OF THE INVENTION

The inventors have searched for and developed resin compositions thatare suitable for injection joining employing the above-describedinventions with better efficiency. Thus, a bonding technology in which avery large number of fine concavities are provided on a metal surfacehas been further advanced and developed. As a result, it has beenestablished not only that simple PBT- or PPS-based compositions thathave a linear thermal expansion coefficients matching those of aluminumalloys are optimum for joining, but also that physical propertiesrelating to crystallinity of the two resins have even strongercorrelation with injection joining. The inventors have also focusedattention on the surface layer of the metal that is to be injectionjoined. The results obtained made it possible to understand specificfeatures of crystallinity of PBT and PPS. Accordingly, it has beeninferred that there is also a possibility of joining by injectionmolding to alloys other than the aluminum alloys subjected to ultrafineetching for which such possibility has heretofore been established. Thisinference will be described below in greater details.

In general, there seems to be two conditions enabling the injectionjoining of a thermoplastic resin to a metal shaped body. The firstcondition is the presence of a metal surface layer having convexitiesand concavities on a micrometer level, this surface with convexities andconcavities being a hard surface, and also the presence of convexitiesand concavities having a shape on an electron microscope level(ultrafiness on a nanolevel). Where large concavities on a micrometerlevel are present, PBT or PPS can penetrate therein in addition to theadsorption of amine molecules. The second condition is that the resin isa crystalline resin with a high crystallization ratio and also highhardness and mechanical strength of the crystallized portion of theresin, these properties being at a level suitable for fixing the resin.More specifically, the resin is PBT or PPS. Where injection molding isperformed under such two conditions, when the molten resin comes intocontact with a low-temperature mold or insert metal that has atemperature by about a hundred degrees lower than the melting point ofthe resin and is rapidly cooled, the crystallization and solidificationof the resin can occur inside the concavities on the metal surface. Insuch case, a strong joining (fixing) of the resin and metal occurs.

The possibility of obtaining a stronger injection joint by improving theabove-described resin composition can be named as a preferred condition(third condition) for injection joining. Thus, the resin compositionhaving crystallinity is improved so that the resin compositioncrystallizes and solidifies during rapid cooling, but the solidificationrate thereof is decreased. Thus, even if the resin is rapidly cooled toa temperature lower than the resin melting point, the seed crystals donot occur from the resin and do not grow, causing solidification,immediately thereafter. An overcooled state is assumed and the resin ismaintained in a molten state for a certain extremely short interval. Itwas assumed that the overcooling time can be delayed by admixing theresin with a certain other resin.

The minimum size of seed crystals, that is, the resin crystals, is about10 nm or larger, and after the seed crystals have appeared and grown,even if they find their way to the entry of ultrafine concavities with adiameter of 20 to 80 nm, apparently it will not be easy for the seedcrystals to reach the farthest zones of the concavities. However, if aresin composition is employed in which seed crystals do not appear atonce during rapid solidification and subsequent crystal growth issomewhat delayed, then the resin will be able to penetrate intoconcavities even when the diameter of concavities is several hundrednanometers. Where the surface inside the concavities is rough, once theresin composition has crystallized and solidified inside theconcavities, it will be difficult to pull the resin composition out, andin this case, an even stronger joint can be obtained.

Magnesium alloys are lighter than aluminum alloys, this being a majorfeature of magnesium alloys, and they also have chemical activity muchhigher than that of aluminum alloys. Immediately after a metal surfacein a magnesium alloy is exposed, e.g. by polishing, a natural oxidationlayer appears, thereby imparting a certain degree of stability. However,the degree of stability or density of the natural oxidation layer aregreatly inferior to those of the oxidation coating layer on aluminumalloys. For example, if a paint coating film or an oil film of acorrosion inhibitor is present on a natural oxidation layer in analuminum alloy, a stability of more than 10 years is ensured in anindoor environment without condensation. By contrast, bulging orcorrosion appears in magnesium alloys in a year or earlier. This isbecause water molecules that diffused through the oil film of coatingfilm also penetrate through the natural oxidation layer and oxidizemagnesium. Thus, in order to use magnesium alloys, they have to becovered with a dense coating film instead of the natural oxidation layerfilm.

More specifically, magnesium alloys are treated by a suitable methodsuch as conversion treatment or electrolytic oxidation, and presentlyconversion treatment is a generally employed method. From the standpointof practical utility, the inventors have established a technologyenabling the injection joining of resins also to magnesium alloyssubjected to conversion treatment. Fortunately, the surface of amagnesium alloy subjected to conversion treatment is covered with ametal oxide, a metal carbonate, or a metal phosphate that is much harderthan the base material that is the metal itself. This matches thecondition relating to the metal surface, of the two above-describedconditions needed for injection joining, that is, that the surface becovered with convexities and concavities of a hard substance.

The present invention is based on the above-described theoreticalinference and attains the below-described objects.

Thus, it is an object of the present invention to provide a composite ofa metal and a resin, in which a resin layer containing PBT or PPS as themain component can be strongly joined to a magnesium alloy and also amethod for manufacturing the composite.

It is another object of the present invention to provide a composite ofa metal and a resin in which a base material composed of a magnesiummetal that has a surface layer subjected to conversion treatment andexcels in corrosion resistance is integrated with a resin compositioncontaining PBT or PPS as the main component and also a method formanufacturing the composite.

It is yet another object of the present invention to provide a compositeof a metal and a resin that has high mass production ability andproductivity when a thermoplastic resin composition containing PBT orPPS as the main component is molded by injection molding and to a methodfor manufacturing the composite.

The present invention employs the following means for attaining theabove-described objects.

The gist of the composite of a metal and a resin in accordance with thepresent invention resides in that the composite comprises: a basematerial comprising a magnesium alloy; a surface layer having, formed ona surface of the magnesium alloy, any one from among a metal oxide, ametal carbonate, and a metal phosphate obtained by preparing an aqueoussolution of at least one kind selected from chromium, manganese,vanadium, calcium, zinc, strontium, zirconium, titanium, and an alkalimetal carbonate and performing a conversion treatment by using theaqueous solution; and a resin layer that has, as a main component, apolybutylene terephthalate resin or a polyphenylenes sulfide resin,which is a thermoplastic resin having crystalline property, and which isintroduced into concavities of the surface layer by injection molding,solidified, and fixed thereto.

A gist of the method for manufacturing a composite of a metal and aresin in accordance with the present invention resides in that themethod comprises: a shaping step of obtaining a shaped part from a castarticle or an intermediate product composed of a magnesium alloy byshaping by mechanical processing; a conversion treatment step of formingone species, selected from a metal oxide, a metal carbonate, and a metalphosphate, on a surface layer of the shaped part; an injection step ofinserting the shaped part subjected to the liquid treatment step into aninjection molding mold and injecting a molten resin compositioncomprising polybutylene terephthalate or polyphenylene sulfide as a maincomponent; and a fixing step of introducing and solidifying by theinjection molding in concavities of the metal oxide or metal phosphateand integrally fixing the shaped part and the resin composition.

The main features constituting the present invention will be describedbelow in greater details.

[Base Material]

The base material as referred to in the description of the presentinvention means a metal portion constituting the composite. Suitablebase materials include commercial products such as alloys for forgingand rolling such as AZ31 system and alloys for casting such as AZ91system that are stipulated in Japanese Industrial Standards (JIS) andall the well-known magnesium alloys. Among magnesium alloys for casting,semiproducts that are formed to the desired shape by an appropriatemolding means such as die casting, thixomolding, or injection molding,or machinery parts obtained by further machining the semiproducts to thedesired shape can be used as the base material. Among alloys for forgingand rolling, sheets, rods, angular members, and tubes that arecommercial products, or parts formed by subjecting them to mechanicalprocessing such as pressing, cutting, or polishing can be used as thebase materials.

[Surface Layer of Base Material (Metal Oxide, Metal Carbonate, or MetalPhosphate)]

The surface layer as referred to in the description of the presentinvention means a metal oxide, a metal carbonate, or a metal phosphateformed on the surface of the base material composed of a magnesiumalloy. It is preferred that the substance constituting the surface layerbe harder than the base material and have a high mechanical strength.Because the surface of magnesium alloys usually has a high ionizationtendency and is easily corroded and oxidized even by moisture from theair, a surface treatment is required. For this reason, a stable layer ofa metal oxide, a metal carbonate, or a metal phosphate containing adissimilar metal is typically formed on the magnesium or magnesium alloysurface by immersing in an aqueous solution of the dissimilar metal saltor an acid, thereby protecting the metal on the inner side fromcorrosion by the presence of the layer.

A layer of a metal phosphate, a metal carbonate, or a metal oxide isformed on the surface of the base material in accordance with thepresent invention by dipping into an aqueous solution. This is becausewhen a magnesium alloy that has a high ionization tendency and is easilycorroded and oxidized even by moisture from the air is immersed in anaqueous solution of a dissimilar metal salt or an acid, a stable layerof oxide, carbonate, or phosphate of the dissimilar metal and/ormagnesium is formed on the surface, thereby protecting the metal on theinner side from corrosion by the presence of the layer. Such animmersion process is called a conversion treatment in the industry ofthe metal surface treatment.

The treatment that also includes degreasing or chemical etchingperformed as a pretreatment for the conversion treatment is often alsoreferred to as the conversion treatment. In accordance with the presentinvention, in order not to mix the two treatments, the term “conversiontreatment” will be used in a narrow meaning of a treatment performed toproduce an anticorrosive layer, the treatment such as degreasing oretching that is performed as a pretreatment for the conversion treatmentwill be referred to as “pretreatment”, and the entire process includingboth the pretreatment and the conversion treatment will be referred toas “liquid treatment”.

A conversion treatment using no chromium is called a non-chromatetreatment, and as far as the inventors know, a manganese-systemtreatment has been mainly used in recent years (see, for example,Japanese Patent Applications Laid-open Nos. 7-126858 and 2001-123274).Further, a method of forming a layer composed of a composite oxide ofaluminum, vanadium, zinc, zirconium, titanium, and the like as ananticorrosive layer on the surface is also known as a non-chromatetreatment (see, for example, Japanese Patent Applications Laid-open Nos.2000-199077). Historically, a chromate treatment method using a chromiumcompound has been used for a long time as a treatment method that excelsin anticorrosive ability.

However, because an aqueous solution of chromic acid is used for thechromate treatment, it creates problems since hexavalent chromiumcausing environmental pollution is contained therein. For this reason, ademand has been created for a conversion treatment method using nochromium. Accordingly, methods using the aforementioned manganese andother metals have been developed. In recent years, methods usingmanganese compounds have attracted attention as methods that can replacethe chromate treatment. The base material employed in accordance withthe present invention can be used when the surface treatment isperformed by any of these methods.

According to the research results obtained by the inventors a morepreferred material satisfies the following requirements: (1) asufficient corrosion resistance, and (2) the presence of convexities andconcavities on the surface layer obtained by conversion treatment andalso the presence of large number of crystal-like substances on thesurface, when viewed under an electron microscope. In accordance withthe present invention, both the condition (1) and the condition (2) haveto be met, but in accordance with the present invention, it was thecondition (2) that was specifically studied. This is because magnesiumor a magnesium alloy preferably has a hard and dense surface layer of ametal oxide, metal carbonate, or metal phosphate. The reason therefor isthat an injection thermoplastic resin having crystallinity penetratesinto the above-described hard and dense surface layer having convexitiesand concavities and crystallizes and solidifies therein, therebyensuring a strong joining force.

Where the hard and dense surface layer obtained by conversion treatmenthas a surface shape with large convexities and concavities on amicrometer level (“with a micron-level roughness”, if phraseddifferently) and nanolevel convexities and concavities on the surface ofconcavities, the resin is grasped by the metal surface, that is, theresin is caught on convexities and concavities of the metal surfacelayer, and a desirable anchor effect is demonstrated. More specifically,it is preferred that two or more plate-like crystals be observed on 1μm², or that needle-like or rod-like crystals cover widely the surfaceor that aggregates having needle-like or rod-like crystals as an outershell be connected to each other and cover the base material surface,those crystals requiring electron microscope observations. Further, itis also preferred that a large number of circular column with a diameterof about 10 nm and a length of about 100 nm be formed, those columnsrequiring electron microscope observations. However, the circularcolumns are not necessarily crystal substances.

When approximately two or more plate-like crystals are observed on 1μm², the plate-like crystals act as walls of convexities andconcavities, and they serve as a means for mechanically strong bonding,thereby effectively increasing the fixing strength. On the other hand,where the needle-like or rod-like crystals cover 30% or more of thesurface, they serve as a natural and strong fixing means composed ofconvexities and concavities that effectively catch the resin and enablea higher injection joining force. Specific methods for implementing eachof the aforementioned steps and how to approach them will be describedbelow.

[Surface Treatment/Pretreatment of Magnesium or Magnesium Alloy]

The pretreatment as referred to in the description of the presentinvention is a pretreatment for forming a surface layer composed of ametal oxide, a metal carbonate, or a metal phosphate on the surface of abase material composed of a magnesium alloy. It is preferred that thebase material composed of magnesium or a magnesium alloy be initiallyimmersed into a degreasing tank to remove foreign matter such as alubricant or chips that have adhered thereto in the course of machining.More specifically, it is preferred that a commercial degreasing agentfor magnesium be dissolved in warm water to a concentration specified bythe manufacturer, a magnesium alloy be immersed therein, and the alloybe thereafter washed with washing water. With the usual commercialproducts, the concentration is 5 to 10%, the liquid temperature is 50 to80° C., and the immersion time is 5 to 10 min. The alloy is thenimmersed into an acidic aqueous solution and etched to dissolve thesurface layer of the magnesium alloy part and remove the contaminants,remaining lubricant, and surfactant residues. The liquid used ispreferably an organic carboxylic acid with pH 2.0 to 5.0; for example, aweakly acidic aqueous solution of acetic acid, propionic acid, citricacid, benzoic acid, or phthalic acid can be used.

Magnesium alloys other than high-purity magnesium with a magnesiumpurity close to 100% contain dissimilar metals. For example, alloys ofAZ31 system and AZ91 system contain 3 to 9% aluminum and about 1% zinc,and aluminum or zinc are hardly dissolved in the etching process usingthe weakly acidic aqueous solution and precipitate on the surface.Therefore a step of dissolving and removing these precipitates andwashing is required.

This is a step that represents the so-called smut removal. Theaforementioned AZ31B and AZ91D alloys are usually subjected to atreatment in which they are first immersed into a weakly basic aqueoussolution to dissolve an aluminum smut (first smut treatment) and thenimmersed into a strong basic aqueous solution to dissolve and remove azinc smut (second smut treatment). In the aforementioned first smuttreatment, a commercial aqueous solution of a degreasing agent foraluminum alloys can be used in a weakly basic range, and the inventorsemployed a method in which such commercial degreasing agent for aluminumis used at a concentration of 5 to 10% and the immersion is performedfor several minutes in an aqueous solution at 60 to 80° C. Further, amethod by which immersion was performed for 5 to 10 min in an aqueoussolution of caustic soda with a concentration of 15 to 25% at 70 to 80°C. was employed for the second smut treatment.

[Surface Treatment/Conversion Treatment of Magnesium or Magnesium Alloy]

The conversion treatment as referred to in the description of thepresent invention serves to form a surface layer composed of a metaloxide, a metal carbonate, or a metal phosphate on the surface of a basematerial composed of a magnesium alloy. Once the above-describedpretreatment has been completed, the conversion treatment that is calledthe main treatment in the liquid treatment is performed. The conversiontreatment is usually implemented as a two-stage conversion treatment,that is, a treatment in which, first, fine etching is performed byimmersing for a very short time in a weakly acidic aqueous solution andthen the conversion treatment for magnesium alloys that represents theconventional technology is implemented in the improved form. In the fineetching process, a weakly acidic aqueous solution of an organiccarboxylic acid, for example, acetic acid, propionic acid, citric acid,benzoic acid, phthalic acid or phenol, phenol derivatives, or the like,with pH 2.0-6.0 can be used, and a very short immersion time of 15 to 40sec is preferred.

Further, the conversion treatment step used in accordance with thepresent invention is basically identical to the well-known conventionalconversion treatment. Thus, this conversion treatment method isprotected by a large number of patents, publicly known, and represents awell-known technology. Accordingly, detailed description thereof isomitted. Such conversion treatment process has also been suggested inwhich corrosion resistance of a magnesium alloy is improved by forming ametal oxide, a metal carbonate, or a metal phosphate in a surface layerby immersing the alloy in an aqueous solution or aqueous suspensioncontaining at least one metal selected from chromium, manganese,vanadium, calcium, zinc, strontium, zirconium, a titanium compound, andan alkali metal carbonate. On the other hand, as far as the inventorsknow, the conversion treatment methods that have been actuallycommercialized include two methods: a chromating method by which thesurface is coated with an oxide of chromium or a chromium oxidecontaining magnesium by immersing in an aqueous solution of a chromicacid system, and a method by which the surface is coated with aphosphoric acid compound of manganese by immersing in an aqueoussolution of manganese phosphate system.

The use of hexavalent chromium is presently barred because of the effectproduced thereby on human body. Accordingly, the latter of theabove-described surface treatment methods becomes a predominant methodand a transition is being made to a process that is referred to as anon-chromate method. For the inventors, the object of the conversiontreatment is not only to impart corrosion resistance, but also to form asurface demonstrating a high mechanical strength in terms of materialdynamics when injection joining is performed. The research resultsobtained by the inventors et al. demonstrate that sufficient corrosionresistance is obtained and an injection joined article with a certainstrength is obtained by using either the conversion treatment of thetype disclosed in the aforementioned patent application or the chromateand non-chromate treatment methods that have been conventionally used.However, when the metal surface of articles with especially goodinjection joining results are observed under an electron microscope,fine crystals are clearly observed and a fine nanolevel repeatingstructure is observed. Accordingly, a fine etching process is preferablyperformed to prepare an article in which crystals or fine repeatingstructure are observed in large amounts under an electron microscope.

A specific example of a conversion treatment process that is consideredas one of the most preferred processes is described below. A magnesiumalloy part subjected to pretreatment is again immersed for 15 to 60 secin an aqueous solution of citric acid hydrate with a concentration of0.1 to 0.5% at a temperature of about 40° C., the alloy part is finelyetched, and then washed with ion-exchange water. An aqueous solutioncontaining potassium permanganate 1 to 5%, acetic acid 0.5 to 2%, andsodium acetate hydrate 0.1 to 1.0% is then prepared at 40 to 60° C. as aconversion treatment liquid, and the magnesium alloy part is immersedtherein for 0.5 to 2 min, washed with water, placed for 5 to 20 min in awarm air drier at 60 to 90° C. and dried. A magnesium alloy part ofbrownish red color covered with a thin layer of manganese oxide isobtained.

On the other hand, an example of a method that is preferred forimplementing the present invention by a chromate treatment method thatis generally considered as the best method in terms of providingcorrosion resistance will be described below. A base material of amagnesium alloy subjected to pretreatment is again immersed for 15 to 60sec in an aqueous solution of citric acid hydrate with a concentrationof 0.1 to 0.5% at a temperature of about 40° C., the base material isfinely etched, and then washed with ion-exchange water. An aqueoussolution containing anhydrous chromic acid (chromium trioxide) 15 to 20%is then prepared at 60 to 80° C. as a conversion treatment liquid, andthe magnesium alloy part subjected to fine etching is immersed thereinfor 2 to 4 min, and washed with water. It is then placed for 5 to 20 minin a warm air drier at 60 to 90° C. and dried. The surface layer issubjected to chromate treatment and a magnesium alloy base material ofgray color is obtained.

[Resin Layer]

The resin layer in accordance with the present invention is a resincontaining PBT or PPS, which is a thermoplastic resin havingcrystallinity, as the main component. Polyamides are also highlycrystalline resins and are not the resins that cannot be used inaccordance with the present invention. However, because they have asomewhat low mechanical strength and can absorb water, they presentlycannot provide sufficient reliability in terms of maintaining a fixingforce for a long time and are not used in accordance with the presentinvention. However, they can be used for certain applications. The resinlayer as referred to in the description of the present invention is aportion obtained by injection molding and although it is described byterm “layer”, it represents a shaped object having a certain thicknessrather than indicating a thin object.

If necessary, fillers and modifiers such as polymers, glass fibers, andcarbon fibers other than PBT or PPS may be admixed to the resin layer inaccordance with the present invention in order to improve variousmechanical properties. A variety of PBT synthesized for injectionmolding can be used as a PBT base resin. On the other hand, the PPS baseresin may have a linear chain structure, or a branched structure may beintroduced thereinto, or it may be subjected to heating in an inactivegas. The resin having a branched structure introduced thereinto or aresin subjected to heating in an inactive gas is preferred.

[Resin Layer (Composition of PPS and Polyolefin)]

The resin layer in accordance with the present invention mainly containsPBT or PPS. However, in the case of PPS, the fixing strength can befurther increased by adding an adequate amount of a polyolefin resin.The reason therefor is supposedly that the crystallization rate duringrapid cooling is reduced by the addition of an adequate amount of thepolyolefin resin. As a result, the resin crystallizes and solidifiesafter it has penetrated sufficiently into the concavities formed on theconversion treatment surface, and the flow of molten resin prior tosolidification corresponds to a certain degree of nanolevel roughness onthe surface of concavities. The resultant effect is that the slip isprevented and the resin is locked, thereby increasing the fixingstrength.

The resin composition composed of PPS having a polyolefin resin addedthereto that is used in accordance with the present invention ispreferably composed of a resin fraction composition containing 70 to 97wt. % PPS and 3 to 30 wt. % polyolefin resin. In order to obtain acomposite with excellent fixing ability, it is even more preferred thata resin fraction composition be obtained that contains 80 to 97 wt. %PPS and 3 to 20 wt. % polyolefin resin. Where the amount of PPS is lessthan 65 wt. % or higher than 97 wt. %, the composite obtained has poorfixing force of the base material and resin layer.

The PPS may be any from the class called PPS. Among such resins, thosewith a melt viscosity of 100-30,000 poise are preferred becauseexcellent molding processability can be attained when the resincomposition is obtained. The melt viscosity is a value obtained bymeasuring with a high-performance flow tester equipped with a die with adiameter of 1 mm and a length of 2 mm at a measurement temperature of315° C. and load of 10 kg. Further, the PPS may be substituted withamino groups or carboxyl groups, or may be copolymerized withtrichlorobenzene or the like during polymerization.

A resin having a linear chain structure, or a branched structureintroduced thereinto, or a resin that is subjected to heating in aninactive gas may be used as PPS. Further, the PPS may be subjected to adeionizing treatment (acid washing, hot water washing, or the like)before or after heating and curing, or the amount of impurities such asions and oligomers may be reduced by performing washing treatment withan organic solvent such as acetone. Furthermore, curing may be advancedby performing heating in an oxidizing gas after the polymerizationreaction is completed.

Usually, well-known commercial ethylene resins and propylene resins maybe used as the polyolefin resins. Among them, from the standpoint ofobtaining a composite with excellent adhesive properties, copolymers ofmaleic anhydride and modified ethylene, copolymers of glycidylmethacrylate and modified ethylene, copolymers of glycidyl ether andmodified ethylene, and copolymers of ethylene and alkyl acrylate arepreferred.

Examples of copolymers of maleic anhydride and modified ethylene includea polymer of maleic anhydride and graft-modified ethylene, a copolymerof maleic anhydride and ethylene, and a terpolymer of ethylene, acrylicacid ester, and maleic anhydride. Among them, from the standpoint ofobtaining an excellent composite, the terpolymer of ethylene, acrylicacid ester, and maleic anhydride is preferred. “Bondine (product name)”(manufactured by Alchema Co., Kyoto, Kyoto Prefecture, Japan) is aspecific example of such terpolymer of ethylene, acrylic acid ester, andmaleic anhydride.

Examples of copolymers of glycidyl methacrylate and modified ethyleneinclude copolymers of glycidyl methacrylate and graft modified ethyleneand copolymers of glycidyl methacrylate and ethylene. Among them, fromthe standpoint of obtaining an excellent composite, copolymers ofglycidyl methacrylate and ethylene are preferred. “Bondfast (productname)” (manufactured by Sumitomo Chemical Co., Ltd., Chuo-ku, Tokyo,Japan) is an example of the copolymer of glycidyl methacrylate andethylene.

Examples of copolymers of glycidyl ether and modified ethylene includecopolymers of glycidyl ether and graft modified ethylene and copolymersof glycidyl ether and ethylene. “Lotryl (product name)” (manufactured byAlchema Co., Kyoto, Kyoto Prefecture, Japan) is an example of anethylene-alkyl acrylate copolymer. In order to obtain an even betterbonding between the base material and resin layer in the composite inaccordance with the present invention, it is preferred that in the resincomposition, 0.1 to 6 part by weight of a polyfunctional isocyanatecompound and/or 1 to 25 parts by weight of an epoxy resin be compoundedwith a total of 100 parts by weight of a resin fraction including PPS 70to 97 wt. % and a polyolefin resin 3 to 30 wt. %.

Commercial non-block and block compounds can be used as thepolyfunctional isocyanate compounds. Examples of polyfunctionalisocyanate compounds include 4,4′-diphenylmethane diisocyanate,4,4′-diphenylpropane diisocyanate, toluene diisocyanate, phenylenediisocyanate, and bis(4-isocyanate phenyl)sulfone. Further,polyfunctional block isocyanate compounds can be compounds that have twoor more isocyanate groups in a molecule and these groups are made to beinactive at room temperature by reacting them with a volatile activehydrogen compound, and the type of polyfunctional block isocyanatecompounds is not particularly limited. Typically they have a structurein which the isocyanate group is masked by a blocking agents such as analcohol, a phenol, ε-caprolactam, an oxime, an active methylenecompound. “Takenate (product name)” (manufactured by Mitsui ChemicalPolyurethane Co., Ltd., Tokyo, Japan) is an example of thepolyfunctional block isocyanate.

Epoxy resins generally known as bisphenol A type resins andcresol-novolak type resins can be used as the epoxy resins. “Epicoat(product name)” (manufactured by Japan Epoxy Resin Co., Ltd., Tokyo,Japan) is an example of a bisphenol A type epoxy resin, and “Epiclon(product name)” (manufactured By Dainippon Ink and Chemicals Co., Ltd.,Tokyo, Japan) is an example of a cresol-novolak type epoxy resin.

[Resin Layer (Composition Obtain by Mixing PBT and PET)]

The resin fraction of the resin layer in accordance with the presentinvention may be a composition obtained by mixing PBT and polyethyleneterephthalate (PET). The appropriate mixing ratio is PBT 5 to 100 wt. %and PET 0 to 35 wt. %.

[Filler]

In the resin used for the resin layer in accordance with the presentinvention, a polybutylene terephthalate resin or a polyphenylene sulfideresin, which is a thermoplastic resin having crystallinity, is used asthe main polymer, but a filler may be mixed with these polymers toimprove mechanical properties thereof. The mixing ratio of the fillermay be 1 to 200 parts by weight of the filler per 100 parts by weight ofthe entire resin fraction of the polyphenylene sulfide resin andpolyolefin resin, or per 100 parts by weight of the entire resincomprising the polybutylene terephthalate resin and polyethyleneterephthalate resin. A fibrous filler, a powdered filler, and aplate-like filler can be used as the filler. Examples of fibrous fillersinclude glass fibers, carbon fibers and aramide fibers. Specificexamples of glass fibers include chopped strands with an average fiberdiameter of 6 to 14 μm. Examples of plate-like and powdered fillersinclude calcium carbonate, mica, glass flakes, glass balloons, magnesiumcarbonate, silica, talc, clay, and ground carbon fibers or aramidefibers. The filler is preferably treated with a silane coupling agent ora titanate coupling agent.

[Method for Manufacturing the Composite]

The composite in accordance with the present invention is preferablymanufactured by an injection joining method, that is, by a method bywhich a base material composed of a magnesium alloy is inserted into aninjection molding mold, the mold is closed, and a resin is injected. Thepreferred manufacture example is described below. Thus, a composite ismanufactured by preparing an injection molding mold, opening the mold,inserting a base material composed of a conversion treated magnesiumalloy that has been obtained by the above-described treatment to oneside of the mold, closing the mold, injecting a thermoplastic resincomposition having PBT or PPS as a resin fraction, solidifying theresin, and opening the mold.

The injection conditions are described below. The mold temperatureproduces little effect on the resin strength of the solidified resin,and from the standpoint of excelling in production efficiency ofcomposites, it is preferred that the mold temperature be equal to orhigher than 100° C., and more preferably equal to or higher than 120° C.On the other hand, the injection temperature, injection pressure, andinjection rate are not different from the usual injection moldingconditions, but to stretch a point, the higher injection rate andinjection pressure are preferred.

As described hereinabove in details, in the composite in accordance withthe present invention, a resin composition part and a base materialcomposed of a magnesium alloy are integrated so that they cannot beeasily peeled off from each other. In such composite, a metal oxide, ametal carbonate, or a metal phosphate is formed on the surface layer ofthe base material. Therefore, the composite excels in corrosionresistance. Further, by molding a thermoplastic resin compositioncontaining PBT or PPS as the main component by injection molding, it ispossible to produce composites composed of a base material containing amagnesium alloy and a resin layer with high mass production ability andproductivity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a structural drawing of an injection molding mold thatillustrates schematically the process of manufacturing a composite of amagnesium alloy piece and a resin composition.

FIG. 2 is an external appearance drawing of a schematically illustratedsingle unit of a composite of a magnesium alloy piece and a resincomposition.

FIG. 3 is a surface photograph of an AZ31B magnesium alloy with anaverage grain size of metal crystals of 7 μm or less that is obtained byusing an aqueous solution of acetic acid as a rough etching agent, usingdilute nitric acid as a fine etching agent, and performing conversiontreatment of a manganese phosphate system.

FIG. 4 is a surface photograph of an AZ31B magnesium alloy with anaverage grain size of metal crystals of 7 μm or less that is obtained byusing an aqueous solution of acetic acid as a rough etching agent, usingcitric acid as a fine etching agent, and performing conversion treatmentof a potassium permanganate system.

FIG. 5 is a surface photograph of an AZ31B magnesium alloy with anaverage grain size of metal crystals of 7 μm that is obtained by usingan aqueous solution of acetic acid as a rough etching agent, usingdilute nitric acid as a fine etching agent, and performing conversiontreatment of a potassium carbonate system.

FIG. 6 is a surface photograph of an AZ31B magnesium alloy (manufacturedby Nippon Kinzoku Kogyo KK, Tokyo, Japan) with an average grain size ofmetal crystals of 7 μm that has been subjected only to a degreasingtreatment.

EXPLANATION OF KEYS 1 magnesium alloy plate 2 movable mold plate 3 fixedmold plate 4 resin composition 5 ping point gate 6 joining surface 7composite

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention are explained below based onexamples thereof. FIG. 1 and FIG. 2 are used as the drawings shared bythe examples. FIG. 1 is a structural diagram of a mold that illustratesschematically an injection molding mold composed of a movable mold plateand a fixed mold plate. FIG. 2 shows an external appearance of acomposite 7 in which a base material 1 and a resin composition 4 arefixed integrally by using the injection molding mold.

The magnesium alloy plate 1 processed to a predetermined shape isinserted between the movable mold plate 2 and fixed mold plate 3 of ametallic mold 10 for injection molding, and the molten resin composition4 is injected from the nozzle and poured into the mold cavity via a pingate 5. The resin composition 4 is fixed to a joining surface 6 havingfine concavities formed on the surface of the magnesium alloy plate 1,and a composite 7 in which the two are integrated is manufactured. Inthe below-described examples, in order to measure the fixing strength ofthe composites 7 manufactured in the examples, a tension is applied tothe magnesium alloy plate 1 and resin composition 4, the joining surface6 thereof is loaded with a shear stress, and the rupture strengththereof is measured to check the fixing force.

EXAMPLES

Examples of the present invention will be described below in greaterdetail. First, evaluation and measurement methods and measurementequipment used for evaluating and measuring composites obtained in thebelow-described examples will be described.

[Evaluation and Measurement Methods and Measurement Equipment]

(a) Melt Viscosity Measurement of Resin

A high-performance flow tester well known as means for measuring meltviscosity and fluid characteristics of various thermoplastic andthermosetting plastics was used to measure the melt viscosity of resins.The melt viscosity was measured at a measurement temperature of 315° C.and under a load of 0.98 Mpa (10 kgf) with a high-performance flowtester “CFT-500 (product name)” (manufactured by Shimazu Corp., Kyotoprefecture, Japan) equipped with a die with a diameter of 1 mm and alength of 2 mm.

(b) X-ray photoelectron analyzer (XPS Observations)

As one surface observation method, observation was conducted with aphotoelectron analyzer (XPS observations) by which the energy ofphotoelectrons emitted from a sample when the sample was irradiated withX rays was analyzed and qualitative analysis of elements was performed.An “Axis-Nova (product name)” (manufactured by Kratos Analytical Co.,Ltd. (England)/Shimazu Corp.) of a system in which a surface with adiameter of several micrometers is observed within a depth range up toseveral nanometers was used as the photoelectron analyzer.

(c) Electron Microscope Observations

An electron microscope was used mainly for observing the base materialsurface. A scanning (SEM) electron microscope “S-4800 (product name)”(manufactured by Hitachi, Ltd., Tokyo, Japan) and “JSM-6700F (productname)” (manufactured by Hitachi Denshi KK, Tokyo, Japan) were used asthe electron microscopes. The observations were performed at 1 to 2 KV.

(d) Scanning Probe Microscope Observations

The aforementioned microscope was mainly used for observing the basematerial surface. The scanning probe microscope uses a probe with aprotruding distal end and the surface stage is enlarged and observed bymoving the probe so as to trace the material surface. “SPM-9600 (productname)” (manufactured by Shimazu Corp., Kyoto prefecture, Japan) was usedas the scanning probe microscope.

(e) Measurement of Joining Strength of Composites

As for the tensile stress, the composite 7 was stretched, a shear forcewas applied, and a shear force at the time of rupture was taken as ashear stress. “Model 1323 (product name)” (manufactured by AikoEngineering KK, Tokyo, Japan) was used as the tensile test machine, andthe shear force was measured at a tension rate of 10 mm/min.

(f) Salt Water Spraying Test

A salt water spraying test was performed to test the composite inaccordance with the present invention for corrosion resistance. A saltwater spraying test machine “SPT-90” (manufactured by Suga Shikenki KK,Tokyo, Japan) that is a material testing device for testing a materialfor corrosion resistance and deterioration by spraying salt water wasused to perform the test.

Preparation Example 1 of PPS Composition

The PPS Preparation Example 1 represents a preparation example in whichPPS and a polyolefin resin were mixed. A total of 6,214 g of Na₂S.2.9H₂Oand 17,000 g of N-methyl-2-pyrrolidone were charged into an autoclavehaving a capacity of 50 L and equipped with a stirrer, and thetemperature was gradually raised to 205° C., while stirring under anitrogen flow, to distill off 1355 g of water. The system was cooled to140° C., then 7160 g of p-dichlorobenzene and 5000 g ofN-methyl-2-pyrrolidone were added and the system was sealed under anitrogen flow. The temperature of the system was raised to 225° C.within 2 h, and the system was polymerized for 2 h at 225° C. Then, thetemperature was raised to 250° C. within 30 min and the polymerizationwas further continued for 3 h at 250° C.

Upon completion of polymerization, the polymer cooled to roomtemperature was isolated with a centrifugal separation machine. Thesolid fraction of the polymer was repeatedly washed with warm water anddried overnight at 100° C. to obtain PPS (referred to hereinbelow as PPS(1)) with a melt viscosity of 280 poise. The PPS (1) was further curedfor 3 h at 250° C. under a nitrogen atmosphere to obtain PPS (referredto hereinbelow as PPS (2)). The PPS (2) thus obtained had a meltviscosity of 400 poise.

A total of 6.0 kg of the PPS (2) obtained, 1.5 kg of a terpolymer ofethylene, acrylic acid ester, and maleic anhydride “Bondine TX8030(product name)” (manufactured by Alchema Co., Kyoto, Kyoto Prefecture,Japan), and 0.5 kg of epoxy resin “Epicoat 1004 (product name)”(manufactured by Japan Epoxy Resin Co., Ltd., Tokyo, Japan) werepremixed homogeneously in a tumbler. Then, the mixture was melt kneadedat a cylinder temperature of 300° C. in a twin-screw extruder “TEM-35B(product name)” (manufactured by Toshiba Kiki KK, Shizuoka Prefecture,Japan), while supplying glass fibers “RES03-TP91 (product name)”(manufactured by Nippon Sheet Glass Co., Ltd., Tokyo, Japan) having anaverage fiber diameter of 9 μm and a fiber length of 3 mm from a sidefeeder so as to obtain a total added amount of 20 wt. %, therebyproducing a pelletized PPS composition (1). The PPS composition (1) is aresin composition in which the polyolefin resin takes 20% of the entireresin fraction, and the epoxy resin fraction takes 7 parts, the entireresin fraction being 100 parts. The PPS composition (1) thus obtainedwas dried for 5 h at 175° C.

Preparation Example 2 of PPS Composition

The PPS composition (1) obtained in the Preparation Example 1 of a PPScomposition was cured for 3 h at a temperature of 250° C. under anoxygen atmosphere to obtain PPS (referred to hereinbelow as PPS (3)).The melt viscosity of the PPS (3) thus obtained was 1800 poise. A totalof 5.98 kg of the PPS (3) obtained and 0.02 kg of polyethylene “NipolonHard 8300A (product name)” (manufactured by Tosoh Corp., Tokyo, Japan)were premixed homogeneously in a tumbler. Then, the mixture was meltkneaded at a cylinder temperature of 300° C. in the twin-screw extruder“TEM-35B” (above-mentioned), while supplying glass fibers “RES03-TP91”having an average fiber diameter of 9 μm and a fiber length of 3 mm froma side feeder so as to obtain a total added amount of 40 wt. %, therebyproducing a pelletized PPS composition (2). This composition is a resincomposition in which the polyolefin resin takes 0.3% of the entire resinfraction. The PPS composition (2) thus obtained was dried for 5 h at175C.

Preparation Example 3 of PPS Composition

A total of 7.2 kg of the PPS composition (2) obtained in the PreparationExample 1 of a PPS composition and 0.8 kg of glycidylmethacrylate—ethylene copolymer “Bondfast E” (manufactured by SumitomoChemical Co., Ltd.) were premixed homogeneously in a tumbler. Then, themixture was melt kneaded at a cylinder temperature of 300° C. in thetwin-screw extruder “TEM-35B” (above-mentioned), while supplying glassfibers “RES03-TP91” having an average fiber diameter of 9 μm and a fiberlength of 3 mm from a side feeder so as to obtain a total added amountof 20 wt. %, thereby producing a pelletized PPS composition (3). Thiscomposition is a resin composition in which the polyolefin resin takes10% of the entire resin fraction. The PPS composition (3) thus obtainedwas dried for 5 h at 175C.

Preparation Example 4 of PPS Composition

A total of 4.0 kg of PPS (2) obtained in the Preparation Example 1 of aPPS composition and 4.0 kg of a terpolymer of ethylene, acrylic acidester, and maleic anhydride “Bondine TX8030 (product name)”(manufactured by Alchema Co., Kyoto, Kyoto Prefecture, Japan), werepremixed homogeneously in a tumbler. Then, the mixture was melt kneadedat a cylinder temperature of 300° C. in the twin-screw extruder“TEM-35B” (above-mentioned), while supplying glass fibers “RES03-TP91”having an average fiber diameter of 9 μm and a fiber length of 3 mm froma side feeder so as to obtain a total added amount of 20 wt. %, therebyproducing a pelletized PPS composition (4). This composition is a resincomposition in which the polyolefin resin takes 50% of the entire resinfraction. The PPS composition (4) thus obtained was dried for 5 h at175° C.

Preparation Example 5 of PBT Composition

A PBT composition (1) containing PBT 47% and glass fibers 38% wasobtained by kneading a commercial PBT resin (Toraycon 1101G45(manufactured by Toray Industries, Inc., Tokyo, Japan) and a PBT resinin use of the twin-screw extruder “TEM-35B”. The PBT composition (1) isa resin composition in which PET takes 24% of the entire resin fraction.The composition thus obtained was dried for 5 h at 130° C.

Example 1

AZ31B magnesium alloy (manufactured by Nippon Kinzoku Kogyo KK, Tokyo,Japan) with a thickness of 0.8 mm and an average metal crystal size onthe surface of 7 μm that was subjected to wet buffing as a final surfaceprocessing was used. The magnesium alloy sheet was cut to a rectangularshape with dimensions of 18 mm×45 mm (thickness 0.8 mm) to obtainmagnesium alloy sheets 1. A through hole was provided in the end portionof the magnesium alloy sheets 1, a copper wire coated with vinylchloride was passed through ten sheets, the copper wire was bent so thatmultiple magnesium alloy sheets 1 were not stacked, and all the sheetswere hung down at the same time.

A commercial degreasing agent “Cleaner 160 (product name)” (manufacturedby Marutekkusu KK, Tokyo, Japan) for magnesium alloys was poured intowater in a degreasing tank to obtain an aqueous solution with aconcentration of 10% at 75° C. The alloy pieces were immersed thereinfor 5 min and washed thoroughly with water. Then, a 2% aqueous solutionof acetic acid with a temperature of 40° C. was prepared in a separatetank and the alloy pieces were immersed therein for 2 min and washedthoroughly with water. Black smut adhered thereto. A 7.5% aqueoussolution of a degreasing agent “NE-6 (product name)” (manufacturedMarutekkusu KK, Tokyo, Japan) for aluminum alloys at a temperature of75° C. was prepared in a separate tank and the magnesium alloy pieceswere immersed therein for 5 min and washed thoroughly with water. It wasseen that the aluminum fraction of the smut was dissolved by the weakbasicity of the liquid. Then, a 20% aqueous solution of caustic soda at75° C. was prepared in another tank and the aforementioned alloy pieceswere immersed therein for 5 min and washed thoroughly with water. It canbe assumed that the zinc fraction of the smut was dissolved thereby. A2% aqueous solution of nitric acid with a temperature of 40° C. was thenprepared in a separate tank, and the magnesium alloy pieces wereimmersed therein for 1.5 min and washed thoroughly with water.

Then, a non-chromate conversion treatment liquid of a manganesephosphate system at 45° C. was prepared in a separate tank. Thus, anaqueous solution containing 2.5% manganese diphosphite, 2.5% phosphoricacid with a concentration of 85%, and 2% triethylamine was prepared, themagnesium alloy pieces were immersed therein for 5 min, washedthoroughly with water, placed for 10 min in a warm air drier at 60° C.,and dried. Upon completion of drying, the copper wire was pulled outfrom the magnesium alloy sheets on a clean aluminum foil, and the sheetswere wrapped in the foil, placed in a polyethylene bag, and sealed forstorage. In this process, the surface to be joined (end portion on theside opposite that where the through holes were provided) was nottouched with fingers or the like.

In 2 days, one piece was observed under an electron microscope. A largenumber of plate-like crystals were seen on the surface, in otherportions, amorphous mater was seen. The length of cavities produced bythe plate-like crystals was 400 to 600 nm, and the depth thereof was 500nm or more. The number of the plate-like crystals that could be observedin a square with a side of 1 μm was 1 to 5, the specific numberdepending on the location. The surface image is shown on an electronmicrograph (see FIG. 3). the remaining magnesium alloy sheets 1 wereremoved in 1 day, the side with the through hole therein was graspedwith a gloved hand to prevent the adhesion of oils, and the sheets wereinserted into an injection molding mold at 140° C. The mold was closed,a PBT resin composition “Toughpet G1030 (product name)” (manufactured byMitsubishi Rayon Co., Ltd.) containing 30% glass fibers was injected atan injection temperature of 260° C. The mold temperature was 140° C.,and a total of 20 integrated composites shown in FIG. 2 were obtained.The resin portion had the dimensions of 10 mm×45 mm×5 mm, and the jointsurface 6 had the dimensions of 10 mm×5 mm and a surface area of 0.5cm².

Four composites were subjected to a tensile rupture test on the moldingday, and the average shear force was 11.8 MPa Further, five compositeswere placed for 1 h into a hot air drier at a temperature of 150° C. onthe molding day and annealed, followed by a tensile test conducted oneday after. The average shear rupture stress was 11.9 MPa. The remaining10 integrated products were coated with a paint “Omac—Silver Metallic(product name)” (manufactured by Ohashi Chemical Industries Co., Ltd.,Osaka, Japan) to a set thickness of 10 μm and baked for 30 min at atemperature of 170° C. Salt water spraying was then conducted for 8 h atnormal temperature by using 1% salt water, followed by washing withwater and drying. No abnormalities in external appearance were observed.

Example 2

An AZ31B alloy sheet with a thickness of 0.8 mm that had an averagemetal crystal grain size of 7 μm was procured. The sheet was cut in thesame manner as in Example 1 to obtain rectangular pieces that wereimmersed for 5 min in an aqueous solution of the degreasing agent“Cleaner 160” with a concentration of 10% at 75° C. and washedthoroughly with water. A 2% aqueous solution of acetic acid at 40° C.was then prepared in a separate tank, and the aforementioned magnesiumalloy sheets 1 were immersed therein for 2 min and washed thoroughlywith water. Black smut adhered thereto. A 7.5% aqueous solution of adegreasing agent “NE-6 (product name)” (manufactured Marutekkusu KK,Tokyo, Japan) for aluminum alloys at a temperature of 75° C. wasprepared in a separate tank and the magnesium alloy pieces were immersedtherein for 5 min and washed thoroughly with water. Then, a 20% aqueoussolution of caustic soda at 75° C. was prepared in another tank and thegroup of magnesium alloy sheets 1 were immersed therein for 5 min andwashed thoroughly with water. The above-described treatment waspretreatment, and the treatment method was identical to that of Example1.

Then, the pieces were immersed for 15 sec in an aqueous solution ofcitric acid with a concentration of 0.5% at a temperature of 40° C. thatwas prepared in a separate tank and were washed with water. An aqueoussolution containing 3% potassium permanganate, 1% acetic acid, and 0.5%sodium acetate at 45° C. was then prepared, and the pieces were immersedtherein for 1 min, followed by thorough washing with water. The pieceswere colored brown and were apparently covered with manganese dioxide.The pieces were then introduced for 10 min into a warm air drier at 60°C. and dried. The copper wire was pulled out from the magnesium alloysheets 1 on a clean aluminum foil, and the sheets were wrapped in thefoil, placed in a polyethylene bag, and sealed for storage. In thisprocess, the surface to be joined (end portion on the side opposite thatwhere the through holes were provided) was not touched with fingers orthe like.

In 2 days, one piece was observed under an electron microscope.Spherical formations with a diameter of 80 to 120 nm that were producedby fine needle crystals were assembled, and these formations aggregatedand joined together, producing periodic concavities and convexities. Theperiod of 0.5 to 1 μm and the depth of concavities was 0.3 to 1 μm. Thenumber of spherical formations per one square with a side of 1 μm was 90to 120. The micrograph is shown in FIG. 4. The remaining magnesium alloysheets 1 were removed in 1 day, the side with the through hole thereinwas grasped with a gloved hand to prevent the adhesion of oils, and thesheets were inserted into an injection molding mold at 140° C. A totalof 10 integrated composites shown in FIG. 2 were obtained in the samemanner as in Example 1. The composites were placed for 1 h into a hotair drier at a temperature of 150° C. on the molding day and annealed,followed by a tensile test conducted one day after. The average shearforce was 11.6 MPa.

Example 3

An AZ31 alloy sheet with a thickness of 0.8 mm that had an average metalcrystal grain size of 7 μm was procured. The sheet was cut in the samemanner as in Example 1 to obtain rectangular pieces that were immersedfor 5 min in an aqueous solution of the degreasing agent “Cleaner 160”with a concentration of 10% at 75° C. and washed thoroughly with water.A 2% aqueous solution of acetic acid at 40° C. was then prepared in aseparate tank, and the aforementioned magnesium alloy sheets 1 wereimmersed therein for 2 min and washed thoroughly with water. Black smutadhered thereto. A 7.5% aqueous solution of a degreasing agent “NE-6(product name)” for aluminum alloys at a temperature of 75° C. wasprepared in a separate tank and the magnesium alloy pieces were immersedtherein for 5 min and washed thoroughly with water. Then, a 20% aqueoussolution of caustic soda at 75° C. was prepared in another tank and thegroup of magnesium alloy sheets 1 were immersed therein for 5 min andwashed thoroughly with water. The above-described treatment waspretreatment, and the treatment method was identical to that of Example1.

Then, the pieces were immersed for 15 sec in an aqueous solution ofcitric acid with a concentration of 0.5% at a temperature of 40° C. thatwas prepared in a separate tank and were washed with water. The pieceswere then immersed for 2 min in an aqueous solution containing 0.12%zircon acetyl acetonate and 0.05% aqueous solution of fluorotitanic acidwith a concentration of 40% at 60° C. The pieces were then placed for 10min in a warm air drier at 60° C. and dried. The copper wire was pulledout from the magnesium alloy sheets 1 on a clean aluminum foil, and thesheets were wrapped in the foil, placed in a polyethylene bag, andsealed for storage. In this process, the surface to be joined (endportion on the side opposite that where the through holes were provided)was not touched with fingers or the like.

Further, the remaining magnesium alloy sheets 1 were removed in 1 day,the side with the through hole therein was grasped with a gloved hand toprevent the adhesion of oils, and the sheets were inserted into aninjection molding mold at 14° C. A total of 10 integrated compositesshown in FIG. 2 were obtained in the same manner as in Example 1. Thecomposites were placed for 1 h on the molding day into a hot air drierat a temperature of 150° C. and annealed, followed by a tensile testconducted one day after. The average shear force was 7.7 MPa (78Kgf/cm²).

Example 4

An AZ31 alloy sheet with a thickness of 0.8 mm that had an average metalcrystal grain size of 7 Mm was procured. The sheet was cut in the samemanner as in Example 1 to obtain rectangular pieces that were immersedfor 5 min in an aqueous solution of the degreasing agent “Cleaner 160”with a concentration of 10% at 75° C. and washed thoroughly with water.A 2% aqueous solution of acetic acid at 40° C. was then prepared in aseparate tank, and the aforementioned magnesium alloy sheets 1 wereimmersed therein for 2 min and washed thoroughly with water. Black smutadhered thereto. A 7.5% aqueous solution of a degreasing agent “NE-6(product name)” for aluminum alloys at a temperature of 75° C. wasprepared in a separate tank and the magnesium alloy pieces were immersedtherein for 5 min and washed thoroughly with water. Then, a 20% aqueoussolution of caustic soda at 75° C. was prepared in another tank and thegroup of magnesium alloy sheets 1 were immersed therein for 5 min andwashed thoroughly with water. The above-described treatment waspretreatment, and the treatment method was identical to that of Example1.

Then, the pieces were immersed for 15 sec in an aqueous solution ofcitric acid with a concentration of 0.5% at a temperature of 40° C. thatwas prepared in a separate tank and were washed with water. The pieceswere then immersed for 5 sec in an aqueous solution containing 2% zincacetyl acetonate, 1% aqueous solution of titanium sulfate with aconcentration of 24%, and 0.1% diammonium fluorozirconate at 70° C. andwashed thoroughly with water. The pieces were then placed for 10 min ina warm air drier at 60° C. and dried. The copper wire was pulled outfrom the magnesium alloy sheets 1 on a clean aluminum foil, and thesheets were wrapped in the foil, placed in a polyethylene bag, andsealed for storage. In this process, the surface to be joined (endportion on the side opposite that where the through holes were provided)was not touched with fingers or the like.

Further, the remaining magnesium alloy sheets 1 were removed in 1 day,the side with the through hole therein was grasped with a gloved hand toprevent the adhesion of oils, and the sheets were inserted into aninjection molding mold at 140° C. A total of 10 integrated compositesshown in FIG. 2 were obtained in the same manner as in Example 1. Thecomposites were placed for 1 h into a hot air drier at a temperature of150° C. on the molding day and annealed, followed by a tensile testconducted one day after. The average shear force was 6.9 MPa.

Example 5

An AZ31B alloy sheet with a thickness of 0.8 mm that had an averagemetal crystal grain size of 7 μm was procured. The sheet was cut in thesame manner as in Example 1 to obtain rectangular pieces that weresubjected to a pretreatment including the degreasing operation. Thepretreatment method was identical to that of Examples 1 to 4. Then, thepieces were immersed for 30 sec in an aqueous solution of citric acidhydrate with a concentration of 0.25% at a temperature of 40° C. thatwas prepared in a separate tank and were washed with water. Themagnesium pieces were then immersed for 5 min in an aqueous solutioncontaining 20% chromic acid at 75° C. and washed thoroughly with water.The pieces were then placed for 10 min in a warm air drier at 60° C. anddried. The copper wire was pulled out from the magnesium alloy sheets 1on a clean aluminum foil, and the sheets were wrapped in the foil,placed in a polyethylene bag, and sealed for storage. In this process,the surface to be joined (end portion on the side opposite that wherethe through holes were provided) was not touched with fingers or thelike.

In 1 day, one piece was subjected to ESCA observations. A large amountof chromium and oxygen were observed. The main component was observed asa composite with trivalent chromium oxide or chromium hydroxide.Further, the magnesium alloy pieces were removed in 1 day, the side withthe through hole therein was grasped with a gloved hand to prevent theadhesion of oils, and the pieces were inserted into an injection moldingmold at 140° C. A total of 20 integrated composites 7 shown in FIG. 2were obtained in the same manner as in Example 1. The composites weredirectly placed for 1 h into a hot air drier at a temperature of 150° C.and annealed, followed by a tensile test conducted one day after. Theaverage shear force was 6.6 MPa. The remaining 10 integrated productswere coated with a paint “Omac—Silver Metallic (product name)” to a setthickness of 10 μm and baked for 30 min at a temperature of 170° C. Saltwater spraying was then conducted for 8 h at 35° C. by using 5% saltwater, followed by washing with water and drying. No abnormalities inexternal appearance were observed.

Example 6

An AZ31B magnesium alloy (manufactured by Nippon Kinzoku Kogyo KK,Tokyo, Japan) with a thickness of 0.8 mm and an average metal crystalsize on the surface of 7 μm that was subjected to wet buffing as a finalsurface processing was cut to obtain rectangular pieces of the sameshape as in Example 1 and the pieces were subjected to pretreatmentincluding the degreasing operation. The pretreatment method wasidentical to that of Examples 1 to 5. Then, the pieces were immersed for30 sec in an aqueous solution of citric acid hydrate with aconcentration of 0.25% at a temperature of 40° C. that was prepared in aseparate tank and were washed with water. The pieces were then immersedfor 5 min in an aqueous solution containing 1% potassium carbonate at70° C. and washed thoroughly with water. The pieces were then placed for10 min in a warm air drier at 60° C. and dried. The copper wire waspulled out from the magnesium alloy pieces on a clean aluminum foil, andthe sheets were wrapped in the foil, placed in a polyethylene bag, andsealed for storage. In this process, the surface to be joined (endportion on the side opposite that where the through holes were provided)was not touched with fingers or the like.

In 1 day, one piece was observed under an electron microscope. Theresults are shown in a micrograph in FIG. 5. A beautiful image in whichintersecting rod-like crystals formed a net-like pattern was observed.On the other hand, the ESCA analysis revealed the presence of magnesium,oxygen, carbon and also microscopic amounts of aluminum, zinc, andsilicon. Because the presence of carbon not in a microscopic amount wasconfirmed, it was supposed that magnesium carbonate is the maincomponent of the surface layer. Further, the remaining magnesium alloypieces were removed in 1 day, the side with the through hole therein wasgrasped with a gloved hand to prevent the adhesion of oils, and thepieces were inserted into an injection molding mold at 140° C. Injectionmolding was performed in the same manner as in Example 1 and a total of20 integrated composites 7 shown in FIG. 2 were obtained. The compositeswere placed for 1 h into a hot air drier at a temperature of 150° C. andannealed, followed by a tensile test conducted one day after. Theaverage shear force was 7.0 MPa.

Example 7

An AZ31B magnesium alloy (manufactured by Nippon Kinzoku KK) with athickness of 0.8 mm and an average metal crystal size on the surface of7 μm was used and the processing preceding pretreatment was performed inthe same manner as in Example 1. Then, the pieces were immersed for 30sec in an aqueous solution of citric acid with a concentration of 0.25%at a temperature of 40° C. that was prepared in a separate tank and werewashed with water. The pieces were then immersed for 10 min in anaqueous solution containing 1% calcium nitrate hydrate, 1% strontiumnitrate hydrate, 0.05% sodium chloride, and 0.95% phosphorus (80%) at65° C. and washed thoroughly with water. The pieces were then placed for10 min in a warm air drier at 60° C. and dried. The copper wire waspulled out from the magnesium alloy pieces on a clean aluminum foil, andthe sheets were wrapped in the foil, placed in a polyethylene bag, andsealed for storage. In this process, the surface to be joined (endportion on the side opposite that where the through holes were provided)was not touched with fingers. In one day, one piece was subjected toESCA.

Magnesium, calcium, strontium, and oxygen were observed in largeamounts. In addition very small amounts of zinc, aluminum, carbon, andsilicon were observed. Oxides of magnesium, calcium, and strontium wereconsidered as the main components. The analytical device used could notclarify whether a single composition or multiple compositions werepresent. Further, the remaining magnesium alloy pieces were removed in 1day, the side with the through hole therein was grasped with a glovedhand to prevent the adhesion of oils, and the sheets were inserted intoan injection molding mold at 140° C. The injection molding was performedin the same manner as in Example 1 and a total of 20 integratedcomposites shown in FIG. 2 were obtained. The composites were placed for1 h into a hot air drier at a temperature of 150° C. on the molding dayand annealed, followed by a tensile test conducted one day after. Theaverage shear force was 7.3 MPa.

Example 8

An AZ31B magnesium alloy with a thickness of 0.8 mm and an average metalcrystal size on the surface of 7 μm was used and the processingpreceding pretreatment was performed in the same manner as in Example 1.Then, the pieces were immersed for 30 sec in an aqueous solution ofcitric acid with a concentration of 0.25% at a temperature of 40° C.that was prepared in a separate tank and were washed with water. Thepieces were then immersed for 2 min in an aqueous solution containing 1%vanadium trichloride at 45° C. and washed thoroughly with water. Thepieces were then placed for 10 min in a warm air drier at 60° C. anddried. The copper wire was pulled out from the magnesium alloy pieces ona clean aluminum foil, and the sheets were wrapped in the foil, placedin a polyethylene bag, and sealed for storage. In this process, thesurface to be joined (end portion on the side opposite that where thethrough holes were provided) was not touched with fingers. In one day,one piece was subjected to ESCA. Vanadium and oxygen were observed inlarge amounts. In addition, a small amount of magnesium and very smallamounts of zinc, aluminum, and silicon were observed. Vanadium oxide oran oxide of vanadium and magnesium were considered as the maincomponents.

Further, the remaining magnesium alloy pieces were removed in 1 day, theside with the through hole therein was grasped with a gloved hand toprevent the adhesion of oils, and the sheets were inserted into aninjection molding mold at 140° C. The injection molding was performed inthe same manner as in Example 1 and a total of 20 integrated composites7 shown in FIG. 2 were obtained. The composites were placed for 1 h intoa hot air drier at a temperature of 150° C. on the molding day andannealed, followed by a tensile test conducted one day after. Theaverage shear force was 7.0 MPa. The remaining 10 integrated productswere coated with a paint “Omac—Silver Metallic (product name)” to a setthickness of 10 μm and baked for 30 min at a temperature of 170° C. Saltwater spraying was then conducted for 8 h at 35° C. by using 5% saltwater, followed by washing with water and drying. No abnormalities inexternal appearance were observed.

Example 9

Example 9 was used to confirm the effect of the PPS resin. “SusteelGS-30 (product name)” (manufactured by Tosoh Corp., Tokyo, Japan), whichis a PPS resin, containing 30% glass fibers was used as a resin forinjection. the injection conditions during molding were as follows:injection temperature 310° C. and mold temperature 140° C. Conditionsother than these injection molding conditions were identical to those ofExample 1. On the molding day, four pieces were subjected to a tensilerupture test. The average shear force was 8.8 MPa (90 Kgf/cm²). Further,on the molding day, five pieces were placed for 1 h in a hot air drierat 170° C. In one day, they were subjected to a tensile test. Theaverage shear force was 9.3 MPa.

The remaining 10 integrated products were coated with a paint“Omac—Silver Metallic (product name)” to a set thickness of 10 μm andbaked for 30 min at a temperature of 170° C. Salt water spraying wasthen conducted for 8 h by using 5% salt water, followed by washing withwater and drying. No abnormalities in external appearance were observed.

Example 10

Example 10 was used to confirm the effect of the PPS resin. Themagnesium alloy pieces were treated in substantially the same manner asin Example 9 and the injection joining was performed in exactly the samemanner as in Example 9. As for the synthetic resin used, the PPScomposition (1) obtained in the Preparation Example 1 of a PPScomposition was used instead of the “Susteel GS-30” employed in Example9. A total of 20 integrated composites 7 shown in FIG. 2 were obtained.The resin portion had a size of 10 mm×45 mm v 5 mm, and the jointsurface 6 had a size of 10 mm×5 mm and an area of 0.5 cm².

On the molding day, four pieces were subjected to a tensile rupturetest. The average shear force was 13.0 MPa. Further, on the molding day,five pieces were placed for 1 h in a hot air drier at 170° C. In oneday, they were subjected to a tensile test. The average shear force was12.8 MPa. The remaining 10 integrated products were coated with a paint“Omac—Silver Metallic (product name)” to a set thickness of 10 μm andbaked for 30 min at a temperature of 170° C. Salt water spraying wasthen conducted for 8 h at 35° C. by using 5% salt water, followed bywashing with water and drying. No abnormalities in external appearancewere observed.

Example 11

Composites were obtained by exactly the same method as that of Example10, except that the PPS composition (3) obtained in Preparation Example3 was used instead of the PPS composition (1) obtained in PreparationExample 1 of a PPS composition. On the molding day, the composite wasannealed for 1 h in at 170° C., and in two days, the shear force wasmeasured in a tensile test machine. The average value was 12.5 MPa. Theremaining 10 integrated products were coated with a paint “Omac—SilverMetallic (product name)” (manufactured by ohashi Chemical IndustriesCo., Ltd., Osaka, Japan) to a set thickness of 10 μm and baked for 30min at a temperature of 170° C. Salt water spraying was then conductedfor 8 h at 35° C. by using 5% salt water, followed by washing with waterand drying. No abnormalities in external appearance were observed.

Example 12

Magnesium alloy pieces were produced, injection molding was performed,and composites were obtained in exactly the same manner as in Example10, except that the PPS composition (2) obtained in Preparation Example2 was used instead of the PPS composition (1) obtained in PreparationExample 1. The composite obtained was annealed for 1 h in at 170° C.This was essentially the test in which a PPS resin compositioncontaining only a filler and PPS containing but a tiny amount ofpolyolefin polymer was used. In one day, it was subjected to a tensiletest. The average shear force for 10 pieces was 9.0 MPa. This value didnot exceed about 70% the numerical value obtained in Example 1, therebydemonstrating the difference between the resin materials.

Example 13

An AZ31B alloy sheet with a thickness of 0.8 mm and an average metalcrystal size on the surface of 7 μm was used. The sheet was cut toobtain rectangular pieces in the same manner as in Example 1. The pieceswere immersed for 5 min in an aqueous solution of a degreasing agent“Cleaner 160” with a concentration of 10% at 75° C. and washedthoroughly with water. Then, a 2% aqueous solution of acetic acid with atemperature of 40° C. was prepared in a separate tank and the alloypieces were immersed therein for 2 min and washed thoroughly with water.Black smut adhered thereto. A 7.5% aqueous solution of a degreasingagent “NE-6 (product name)” for aluminum alloys at a temperature of 75°C. was prepared in a separate tank and the magnesium alloy pieces wereimmersed therein for 5 min and washed thoroughly with water. Then, a 20%aqueous solution of caustic soda at 75° C. was prepared in another tankand the group of the aforementioned alloy pieces were immersed thereinfor 5 min and washed thoroughly with water. The treatment described wasa pretreatment, and the treatment method was identical to that ofExample 1.

The pieces were then immersed for 15 sec in an aqueous solution ofcitric acid hydrate with a concentration of 0.5% at a temperature of 40°C. that was prepared in a separate tank and were washed with water. Anaqueous solution containing 3% potassium permanganate, 1% acetic acid,and 0.5% sodium acetate hydrate and having a temperature of 45° C. wasthen prepared, and the pieces were immersed therein for 1 min and thenwashed thoroughly with water. The pieces were colored brown. The pieceswere then placed for 10 min in a in a warm air drier at 60° C. anddried. The copper wire was pulled out from the magnesium alloy pieces ona clean aluminum foil, and the sheets were wrapped in the foil, placedin a polyethylene bag, and sealed for storage. In this process, thesurface to be joined (end portion on the side opposite that where thethrough holes were provided) was not touched with fingers.

In 2 days, one piece was subjected to ESCA observations. A large amountof manganese and oxygen were observed. In addition, very small amountsof magnesium, zinc, aluminum, carbon, and silicon were observed.Manganese oxide containing manganese dioxide as the main components wasassumed to be a main component. This assumption was supported by a browncolor tone. Further, the remaining magnesium alloy pieces were removedin 1 day, the side with the through hole therein was grasped with agloved hand to prevent the adhesion of oils, and the pieces wereinserted into an injection molding mold at 140° C. A total of 20integrated composites 7 shown in FIG. 2 were obtained in exactly thesame manner as in Example 1.

On the molding day, the composites were placed for 1 h into a hot airdrier at a temperature of 170° C. and annealed, followed by a tensiletest conducted one day after. The average shear force was 15.1 MPa. Theremaining 10 integrated products were coated with a paint “Omac—SilverMetallic (product name)” to a set thickness of 10 μm and baked for 30min at a temperature of 170° C. Salt water spraying was then conductedfor 8 h at 35° C. by using 5% salt water, followed by washing with waterand drying. No abnormalities in external appearance were observed.

Example 14

AZ31B alloy pieces were pretreated in exactly the same manner as inExample 13. The pieces were then immersed for 1 min in an aqueoussolution of citric acid hydrate with a concentration of 0.25% at atemperature of 40° C. that was prepared in a separate tank and werewashed with water. An aqueous solution containing 2% potassiumpermanganate, 1% acetic acid, and 0.5% sodium acetate hydrate and havinga temperature of 45° C. was then prepared, and the pieces were immersedtherein for 1 min and then washed thoroughly with water. The pieces werethen placed for 15 min in a in a warm air drier at 60° C. and dried. Thecopper wire was pulled out from the magnesium alloy pieces on a cleanaluminum foil, and the sheets were wrapped in the foil, placed in apolyethylene bag, and sealed for storage.

In 2 days, one piece of these was removed and inserted in an injectionmolding mold at 140° C., followed by the injection of PBT composition(1). The injection molding conditions were identical to those ofExample 1. The integrated object shown in FIG. 2 was obtained. It wasplaced for 1 h into a hot air drier at a temperature of 150° C. andannealed, followed by a tensile test conducted one day after. Theaverage shear force was 15.8 MPa.

The remaining 10 integrated products were coated with a paint“Omac—Silver Metallic (product name)” to a set thickness of 10 μm andbaked for 30 min at a temperature of 170° C. Salt water spraying wasthen conducted for 8 h at 35° C. by using 1% salt water, followed bywashing with water and drying. No abnormalities in external appearancewere observed.

Comparative Example 1

Comparative Example 1 was used to confirm the effect of the conversiontreatment of Example 1. Magnesium alloy sheets 1 were obtained inexactly the same manner as in Example 1, except that the conversiontreatment was not performed. Thus, AZ31B magnesium alloy sheets 1 wereproduced, degreased, roughly etched, treated to remove smut, finelyetched, and treated to remove smut. In fact, only the non-chromatetreatment with a manganese phosphate system was not performed. In 2days, the remaining magnesium alloy sheets 1 were removed, the side withthe through hole therein was grasped with a gloved hand to prevent theadhesion of oils, and the sheets were inserted into an injection moldingmold at 140° C.

The injection molding mold was closed and a PBT resin identical to thatused in Example 1 was injected at an injection temperature of 260° C.The mold temperature was 140° C., and 14 integrated composites shown inFIG. 2 were obtained. The resin portion had a size of 10 mm×45 mm×5 mm,and the joint surface 6 had a size of 10 mm×5 mm and an area of 0.5 cm².On the molding day, the composites were annealed for 1 h at 150° C. andthen four composites were subjected to a tensile rupture test. theaverage shear force was 7.4 MPa.

The remaining 10 integrated products were coated with a paint“Omac—Silver Metallic (product name)” to a set thickness of 10 μm andbaked for 30 min at a temperature of 170° C. On the next day, the coatedproducts were sprayed with salt water for 8 h at normal temperature byusing 1% salt water, followed by washing with water and drying. Finebulging of the coated film was observed over the entire integratedproduct. All ten composites were subjected to a tensile rupture test.The shear force had an average value of 4.9 MPa (50 Kgf/cm²). A brittleoxide film penetrated even onto the rupture surface, and when noconversion treatment was performed, the coating alone was confirmed tomake the composite unsuitable for practical use.

Comparative Example 2

Magnesium alloy pieces were obtained in exactly the same manner as inExample 1, except that the conversion treatment was not performed. Thus,AZ31B magnesium alloy pieces were produced, degreased, roughly etched,treated to remove smut, finely etched, and treated to remove smut. Infact, only the non-chromate treatment with a manganese phosphate systemwas not performed. No crystalline matter was observed under an electronmicroscope, and the surface was natural oxide layer of magnesium.

In 2 days, the remaining magnesium alloy pieces were removed, the sidewith the through hole therein was grasped with a gloved hand to preventthe adhesion of oils, and the pieces were inserted into an injectionmolding mold at 140° C. The mold was closed and PPS (1) obtained in thePreparation Example 1 was injected at an injection temperature of 310°C. The mold temperature was 140° C., and 14 integrated composites shownin FIG. 2 were obtained. The resin portion had a size of 10 mm×45 mm×5mm, and the joint surface 6 had a size of 10 mm×5 mm and an area of 0.5cm². On the molding day, four composites were subjected to a tensilerupture test. The average shear force was 11.3 MPa.

The remaining 10 integrated products were coated with a paint“Omac—Silver Metallic (product name)” to a set thickness of 10 μm andbaked for 30 min at a temperature of 170° C. On the next day, the coatedproducts were sprayed with salt water for 8 h at 35° C. by using 5% saltwater, followed by washing with water and drying. Fine bulging of thecoated film was observed over the entire integrated product. All tencomposites were subjected to a tensile rupture test. The shear force hadan average value of 7.0 MPa. A brittle oxide film penetrated even ontothe rupture surface, and when no conversion treatment was performed, thecoating alone was confirmed to make the composite unsuitable forpractical use.

Comparative Example 3

An attempt was made to manufacture composites by the same method as thatof Example 10, except that the PPS composition (4) of PreparationExample 4 of a PPS composition was used instead of the PPS composition(1) of Preparation Example 1 of a PPS composition. Thus, a test wasperformed by using a PPS resin composition containing a very largeamount of a polyolefin polymer. Such resin material should be called apolyolefin material rather than a PPS material. A large amount of gaswas generated during molding, the injection molding was difficult toperform, and the operations were terminated.

Comparative Example 4

An AZ31B magnesium alloy (manufactured by Nippon Kinzoku Kogyo KK,Tokyo, Japan) with a thickness of 0.8 mm and an average metal crystalsize on the surface of 7 μm that was subjected to wet buffing as a finalsurface processing was used. It was cut to 18 mm×45 mm pieces. A throughhole was provided in the end portion, a copper wire coated with vinylchloride was passed through the pieces, and copper wire was bent so thatmultiple magnesium alloy pieces were not stacked. A total of ten pieceswere hung down at the same time.

A commercial degreasing agent “Cleaner 160” for magnesium alloys waspoured into water at 65° C. and dissolved in a degreasing tank to obtaina concentration of 10%. The alloy pieces were immersed therein for 5 minand washed thoroughly with water, and dried for 15 min at 67° C. Thus,this test was designed to verify the joining strength in the case thealloy was subjected only to the degreasing treatment. After 3 days, onepiece was observed under an electron microscope. The micrograph thereofis shown in FIG. 6. After one more day has passed, the alloy piece wasinserted into an injection molding mold at 140° C., and a PPScomposition (1) was injected. The injection molding conditions wereidentical to those of Example 10. When the injection molding mold wasopened, an integrated article was not obtained.

Comparative Example 5

A test was performed in exactly the same manner as in ComparativeExample 4, except that the resin used was changed from the PPScomposition (1) to the PBT composition (1) and an injection moldingcondition was the same as that in Example 1. In this case, too, when theinjection molding mold was opened, the resin molding and magnesium alloypiece were not integrated.

Table shown below summarizes the results obtained in the above-describedexamples and comparative examples.

TABLE 1 Summary of Results Obtained in Examples and Comparative ExamplesConversion Base treatment Resin Strength material liquid (main) (Mpa)Notes Example 1 AZ31B Manganese PBT 11.9 phosphate system Example 2AZ31B Potassium PBT 11.6 Surface permanganate has spherical formationsExample 3 AZ31B Zirconium PBT 7.7 acetyl acetonate, titanium fluorideExample 4 AZ31B Zinc acetyl PBT 6.9 acetonate, titanium sulfate Example5 AZ31B Chromic acid PBT 6.6 Example 6 AZ31B Potassium PBT 7.0 carbonateExample 7 AZ31B Calcium PBT 7.3 nitrate hydrate, strontium nitratehydrate Example 8 AZ31B Vanadium PBT 7.0 trichloride Example 9 AZ31BManganese PPS 9.3 Salt water phosphate test is system possible Example10 AZ31B Manganese PPS, 12.8 phosphate olefin system system Example 11AZ31B Manganese PPS, 12.5 phosphate olefin system system Example 12AZ31B Manganese PPS 9.0 Small phosphate amount of system polyolefinsystem is added Example 13 AZ31B Potassium PBT 15.1 permanganate Example14 AZ31B Potassium PBT, PET 15.8 permanganate Comparative AZ31B Onlyetching PBT 7.4 Salt water Example 1 and treating test is to removeimpossible smut Comparative AZ31B Only etching PPS 11.3 Salt waterExample 2 and treating test is to remove impossible smut ComparativeAZ31B Manganese PPS, Molding is Small Example 3 phosphate olefinimpossible amount of system system polyolefin system is addedComparative AZ31B Only PPS, No fixing Example 4 degreasing olefin systemComparative AZ31B Only PBT, PET No fixing Example 5 degreasing

INDUSTRIAL APPLICABILITY

The composite of a metal and a resin and a method for manufacturing samein accordance with the present invention can be used for casings ofelectronic devices, housings of domestic electric appliances, structuralcomponents, machinery parts, and the like. In particular, becausemagnesium alloys have higher strength and bending elastic modulus perunit weight than aluminum alloys or ferrous metals, they are widelyemployed for structural materials and parts. Using these properties, itis possible to expect the application thereof to mobile electronicdevice, body parts of aircrafts, and automobile parts for which lightreduction is required.

The invention claimed is:
 1. A composite of a metal and a resin,comprising: a base material comprising a magnesium alloy; a surfacelayer of a metal oxide on the surface of the base material having asurface configuration such that spherical formations with a diameter of80 to 120 nm are aggregated to form periodic irregularities with aperiod of 0.5 to 1 μm and obtained by performing a chemical etchingtreatment of the base material, preparing an aqueous solution for amanganese-system conversion treatment and performing a conversiontreatment by using the aqueous solution; and a resin part formed andjoined to the base material by injection molding and comprising, as amain component, a thermoplastic resin composition having crystallineproperty, which comprises polyphenylene-sulfide with content ratio of 70to 97 wt. % and modified polyolefin resin with content ratio of 3 to 30wt. % and which penetrates into fine concavities with nanometer-ordersize of the surface layer through injection molding, to be solidifiedand fixed thereto.
 2. The composite of a metal and a resin according toclaim 1, wherein the resin layer further comprises 0.1 to 6 parts byweight of a polyfunctional isocyanate compound and/or 1 to 25 parts byweight of an epoxy resin per 100 parts by weight of the entire resincomponent comprising the polyphenylene-sulfide resin and the polyolefinresin.
 3. The composite of a metal and a resin according to claim 1,wherein the modified polyolefin resin is a polyolefin resin of at leastone kind selected from a maleic anhydride-modified ethylene copolymer, aglycidyl methacrylate-modified ethylene copolymer, and an ethylene-alkylacrylate copolymer.
 4. The composite of a metal and a resin according toclaim 1, wherein the modified polyolefin resin is a polyolefin resin ofat least one kind selected from an ethylene-acrylic acid ester-maleicanhydride terpolymer and an ethylene-glycidyl methacrylate dipolymer. 5.The composite of a metal and a resin according to claim 1, wherein themanganese-system conversion treatment is a treatment using an aqueoussolution containing potassium permanganate.